Hc-co(ch,cho)xh

ABSTRACT

PHOSPHORUS-CONTAINING COMPOUNDS WHICH ARE USEFUL IN THE PREPARATION OF POLYURETHANES AND WHICH ARE DERIVED FROM (1) PHOSPHORUS COMPOUNDS CONTAINING AT LEAST ONE ACTIVE FUNCTION (2) ALKYLENE OXIDES OR EPIHALOHYDRIN AND (3) DICARBOXYLIC ACID ANHYDRIDES ARE PROVIDED. AMONG THE COMPOUNDS ARE THOSE PREPARED BY REACTING A DICARBOXYLIC ACID ANHYDRIDE WITH A PHOSPHORUS ACID WHICH HAS BEEN PARTIALLY OR COMPLETELY REACTED WITH AN ALKYLENE OXIDE OR EPIHALOHYDRIN, FOLLOWED BY REACTION OF THE CARBOXYL GROUP THUS FORMED WITH ADDITIONAL ALKYLENE OXIDE OR EPIHALOHYDRIN. METHODS FOR PREPARATION OF THE COMPOUNDS ARE ALSO PROVIDED.

United States Patent Re. 27,969 Reiasued Apr. 16, 1974 Office Matterenclosed in heavy brackets [1 appears in the original patent but formsno part of this reissue specification; matter printed in italicsindicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE Phosphorus-containing compounds which areuseful in the preparation of polyurethanes and which are derived from(1) phosphorus compounds containing at least one active function, (2)alkylene oxides or epihalohydrin and (3) dicarboxylic acid anhydridesare provided. Among the compounds are those prepared by reacting adicarboxylic acid anhydride with a phosphorus acid which has beenpartially or completely reacted with an alkylene oxide or epihalohydrin,followed by reaction of the carboxyl group thus formed with additionalalkylene oxide or epihalohydrin. Methods for preparation of thecompounds are also provided.

This invention relates to new and novel phosphorus compounds and to aprocess for their manufacture. More particularly, the invention isconcerned with compounds prepared from compounds of phosphoruscontaining at least one active site, dicarboxylic acid anhydrides,alcohols, phenols, and alkylene oxides or epihalohydrins. Specificallythe compounds of the present invention are represented by the formulas Ris a member of the group consisting of (lower) alkoxy (lower) alkyl,alkyl containing from 1 to 18 carbon atoms, aryl, alkyl-substitutedaryl, wherein the alkyl contains from 1 to 18 carbon atoms,chloro-substituted aryl bromo-substituted aryl, aralkyl, and

wherein D and x are hereinafter defined;

R is a member of the group consisting of hydrogen,

alkyl containing from 1 to 18 carbon atoms, and pheny R" is a member ofthe group consisting of alkyl containiug from 1 to 13 carbon atoms and(lower) alkoxy (lower) alkyl;

A is the nucleus of a member of the group consisting of aromaticdicarboxylic anhydrides and aliphatic dicarboxylic anhydrides;

D is a member of the group consisting of hydrogen, lower alkyl andchloro (lower) alkyl;

F is a member of the group consisting of hydrogen and G is a member ofthe group consisting of hydrogen and wherein R and R are as hereinabovedefined and a and b are as hereinafter defined;

a and b are each 0 to 2 their sum being 2;

r, s, and t are, respectively, 0 to 2, 0 to 2 and 1 to 3, their sumbeing 3;

W is the hydrocarbyl nucleus of a polyhydroxy compound containing from 2to 4 hydroxyls;

x has an average value of from about 1.0 to about 5.0;

and

z is an integer corresponding to the number of hydroxyls in W.

provided that when G is hydrogen, .1 is at least I.

There are several categories of chemicals which fall within the abovegeneric definition, but for purposes of illustrating this invention,three will be discussed in general and specific terms, particularly withrespect to methods for their preparation.

The simplest class of products falling within the above genericdefinitions may be represented by the compound 0 0 (CHIsCIHOLi (OCHa):

which is prepared by (1) reacting phthalic anhydn'de with an equimolarquantity of methyl alcohol, (2) neutralizing the acid function thusformed with propylene oxide, and (3) reacting this neutral product withdimethyl phosphorochloridate, in the presence of a halogen acidacceptor, if desired. Whereas the particular phosphorus-containingcompound shown is a derivative of phosphoric, the class, as is evidentfrom the generic formulas shown above, includes phosphorus-containingcompounds which have one or two carbon-to-phosphorus bonds in themolecule,

The second class of compounds contemplated by the present invention isprepared by the simultaneous reaction of an aromatic or aliphaticdicarboxylic acid anhydride, a compound of phosphorus containing atleast one reactive hydrogen atom, and an alkylene oxide. The compoundsof this class are monomeric with respect to each reactive hydrogen andanhydride, they are neutral, and they may contain as many anhydrides asthere are active hydrogens in the phosphorus compound used. Thefollowing members will illustrate the scope contemplated by this secondclass.

(CHICHO] H and the same type of compound wherein one [or both] of theright-hand phosphorous ester portions may be replaced with one [or two]aromatic or aliphatic groups bound to carbon.

O(CHzCHO);H

O CH: CH; O atimolmmms toa The compounds of this class my be prepared ina three-step process, involving (1) the oxyalkylation of the phosphoruscompound, (2) the reaction of the product thus formed with theanhydride, and (3) the neutralization of this product with additionalalkylene oxide. For example, (1) abve can be prepared using thethree-step process essentially in the following manner:

0 (CHaO):P(O)O(CHgCHO);

(b) CH; CHCH,

O (C s h 0 (FHOh It is obvious from this series of steps that onlydiscrete molecules are possible, since under normal conditions thecarboxyl groups formed in step (b) will not react with the remaininganhydride to open its ring, nor with a1coholic OH groups present in themixture to form additional polyester links by splitting out water.

As mentioned previously, these compounds may be prepared by thesimultaneous reaction of a phosphorus compound, an anhydride, and analkylene oxide. The products formed in this manner are similar to thoseobtained using the above-outlined three-step process. This wassurprising in view of the normally expected sequence of reactions in asystem containing the named components, since the very nature of thesereactions would logically exclude any expectation of discrete chemicals.

It is well-known that alkylene oxides will react with the acid functionsof a phosphorus acid to yield a compound which is terminated with one ormore hydroxyl groups. It is further known that the active hydrogen thusformed will react with an anhydride, opening its ring to give an estergroup and a carboxyl group. In the presence of alkylene oxide, one wouldexpect this carboxyl to compete with the phosphorus acid for oxideaddition. If this were to occur there would exist a different estercapable of reacting with the anhydride present, the ester portion beingattached to one position of the ruptured ring and another carboxyl beingformed at the other position. If this process were repeated many timesduring the course of a reaction involving the named materials, one wouldobtain a polymeric product, not one which is essentially monomeric, ieone similar to a product obtained from the three step [stop] processgiven hereinbefore.

The single-step, or simultaneous, process for the production of thechemicals of this class does not necessarily mean that all of theanhydride, phosphorus compound and alkylene oxide are brought togetherinitially. This may be impracticable in view of the extreme reactivityof the phosphorus acid and oxide. Thus, the preferred reaction orderinvolves mixing the anhydride and phosphorus acid, followed by thestep-wise addition of oxide to this mixture. It will be obvious,however, that any equivalent variation of this, such as mixing anhydrideand oxide, with subsequent addition of phosphorus acid to this mixture,can be used and still be within the one-step process contemplated by thepresent invention.

In practicing the preferred form of the process for producing thissecond class of chemicals, a dicarboxylic acid anhydride and acid ofphosphorus are placed together within a pressure apparatus. Alkyleneoxide is then fed into the mixture, the addition thereof is begun atroom temperature, and the heat of reaction is allowed to carry thetemperature to -95 C., the temperature of reaction being maintained ator near the top of this range until all of the oxide is added.Alternatively, the mixture may be heated to [form] from 70 to C. priorto beginning addition of oxide. Upon the completion of this initialreaction, excess oxide, preferably in a total molar ratio of (2 to 2.5)times the number of acid functions to be neutralized is fed into thereaction vessel, the temperature is raised to l20l25 C. and maintainedthere for from 1 to 8 hours to complete neutralization of the carboxylhydrogens formed upon the reaction between the alkoxylated acid andanhydride. Excess oxide is removed in vacuo. The mixture is continouslystirred throughout the reaction.

The temperature of reaction may be as high as about 160 C. during theprocess without any adverse eflects on the desired product, but isusually, and preferably, within the range of about 80 to about C. Thetimes to complete the reaction will vary with the temperature used, andwith the kind and amount of anhydride employed, but will generally runfrom about 1 to 8 hours. If the temperature of the reaction is permittedto exceed about C., it will have a detrimental eifect on the product.Since it is known that high temperatures are required for esterwhereinR, R, a and b is as defined hereinbefore and Hal is halogen. Generally,this is done by reacting a quantity of equivalent to the amount ofhydroyls present in the compound in question.

Included among the dicarboxylic acid anhydrides which are suitable forthe purposes of this invention are:

ALIPHATIC ANHYDRIDES Adipic, azelic, glutaric, suheric, itaconic,pimelic, suecinic, acetonedicarboxylic, maleic, chloromaleic,dichioromaleic (and other halo-substituted aliphatic), dimethylmaleic,n-decylsuccinic (and other alkylsubstituted anhydrides wherein the alkylhas from 1 to 12 carbon atoms), hydrophthalic (as dihydrophthalic,tetrahydrophthalic and hexahydrophthalic), endomethylene phthalic,camphoric, 5-norbornene-2, and chlorendic[l,4,5,6,7,7-hexachlorobicyclo- (2,2,2) -5-heptene-2,S-dicarboxylic]AROMATIC ANHYDRIDES Phthalic, 3-chlorophthalic, 4-chlorophthalic,tetrachlorophthalic, 3-bromophthalic, 4-bromophthalic,tetrahromophthalic, S-iodophthalic, 4-iodophthalic (and otherhalo-substituted phthalics), 3-nitrophthalic (and othernitro-substituted phthalics), B-methylphthalic, 4-methylphthalic (andother alkyl-substituted), homophthalic, and naphthalic.

Included among the phosphorus acids are:

PHOSPHORUS ACIDS [Unsubstituted phosphoric, pyrophosphoric, andpolyphosphoric acids] acids PHOSPHONIC ACID RP( 0) 0H OR where R ismethyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl,octadecyl, and phenyl;

RP(O) 0H(OR') where R and R are selected from methyl, ethyl, propyl,butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, octadecyl, andphenyl.

6 PHOSPHINIC ACID lt wmn where R is methyl, ethyl, propyl, butyl,pentyl, hexyl, octyl, decyl, dodecyl, and octadecyl;

R,P(0)OH where R is methyl, ethyl, propyl, butyl, pentyl, hexyl, andphenyl.

The following examples will illustrate the compounds of the presentinvention. It is to be understood, however, that they are merely for thepurpose of illustration, and are not necessarily to limit the invention.

EPOXIDES o eth c!!!) where D is hydrogen, CH cgH5 and CICH,, that is,

where the epoxides may be ethylene oxide, propylene oxide, butyleneoxide and epichlorohydrin.

EXAMPLE 1 t i1 ):P(O)Cl I ocnHu Ethoxylated tridecyl acid phthalate,344.6 parts, pyridine, 69.6 parts, and hexane, 395 parts, were placed inmeans for cooling. 274.2 parts of bis(2-ethylhexyl) phosphorochloridatewas added to this solution, with stirring, at 10 C. or below. When theaddition was completed, the cooling means was removed, and the mixturewas stirred for 2 hours and 15 minutes, after which it was washed with1000 parts of water, then with 500 parts of 8% sodium carbonatesolution, and finally with two portions of water, 1000 parts of eachwash.

The hexane was removed in vacuo to a final pot temperature of 125 C. anda final pressure of 10 mm. of Hg. The product, a clear, light goldenyellow liquid, had the following properties:

Total acid 3.2 mg. KOH/g. P(calculated) 4.2%; P (found) 4.3%

EXAMPLE 2 0 can (CHIO)2P(O)C1 G 0(CH3CH1) mi 0 0 C li l 4101EO(CHQCHIO)LIIP(O) (0011;): N/

In a process similar to that of Example 1, 430.7 parts of theethoxylated acid phthalate, 151.7 parts of dimethyl phosphorochloridate,87.0 parts of pyridine, and 378 parts of benzene gave a product whichwas light yellow in color, and which had a total acid of 2.5 mg. KOH/g.Theoretical phosphorus was calculated as 5.8%; 5.1% phosphorus wasdetected in the product.

The following table summarizes other compounds which have been preparedusing a process similar to that of Example 1.

Totai acid, P, percent mg. KOHI Density, Refractive Compound gm. 20/4index at C. Calcd. Found Example:

3 O 0. 62 1. 289 1.4994 at 28 OCH;

i (CHzC H: )M1 3):

EOC H C 0(CH1CI'I10)Q.I3P(O) (0 C 2):

5 (a? 0. 44 1. 163 1.4840 at 27 COC|H11 E0 (CH:CHaO)i.aP(O) (0 CH1):

6 O 2. 39 1. 243 1.495 at 27.5

C O (CH1CHO)Q.55P(0) (0 CH1): 1; E

7 (I) 1. 50 1.198 1.4.878 at 27 doom.

C ()(CH2CHO)1.|"P(0)(OCH1)| ti 3m.

8 (I) 3.59 1. 134 1.4846 at 27 (EOCuHu ("30 (CH:CHO):P(O) (OCHa):

G0 CisHar (?O(CH=CHO)1.5P(O) (0 CH1);

(a 7.1 1.024 1.4726 at 24.--- 4.20 4. 38

C OCn M I aCHO)I-M J 01E102 11 (H) 0. 54 1. 228 1.4877 at C O CHzCHrO(34 E0(CH2CH:O)1.MP(O) (0 CH2):

6O Phthalic anhydride, 145.2 parts and 322.4 parts of his EXAMPLE 12(Z-ethylhexyl) hydrogen phosphate were placed into a pressure apparatusequipped with a stirrer, thermometer and means for adding oxide. Themixture was heated to 70 C., and while stirring, 232.3 parts ofpropylene oxide was added over a period of 8 minutes. During theaddition of oxide, the temperature increased to a maximum of 91 (1., andthe pressure increased to 26 p.s.i. Immediately after completing theaddition, the temperature dropped to 68 C. During a two hour stirringperiod, the temperature was carried, by external heating means, to amaximum of 102 C., the last one hour being within the range of -102" C.The maximum pressure, which increased gradually over this period, was 69p.s.i.

At the end of this heating period, the product had an acid number of 126mg. KOH/gm. The product was heated for a further hour at 119-423 C.,after which the acid content was 0.9 mg. KOH/gm. Excess oxide wasremoved in vacuo, the final pot temperature being 110' C., at mm. Hg.

The product, a golden brown, viscous liquid, had the followingproperties:

OH (calculated), 89 mg. KOH/gm.; OH (found), 104.5

10 EXAMPLE 20 mg. KOH/gm. 0 P (calculated), 5.02%; P (found), 4.96%. 10g Q J I 1 Density 20/4, 1.093. Refractive index at 26 C., 1.4790.

00 CH CHO B Total acid 0.14 mg. KOH/gm. 1

In a manner similar in all material aspects to Example 12, the followingcompounds were prepared: where x=2.25 (average).

0.. 11 1113. ac xofi P,peree t x, i fin Density, Refractive 1165/ ExCompound avg. Caled. Found Calcd. Found /4 index 116C. gm. 1a.--- 0 1.20 05 112.5 5.35 5.17 1.113 1.1810 at a 12 o( 0H|cH10),P(0) (0011111):

CO(CH1CH1O);H

14....- Br 0 1.34 61.5 7014 3.47 3.48 1. 536 1.5285 at 25.5.. 0.05

mowmcmohno (00111.1),

B1 CO(CH:CH:0);H

15-.- 0 0H, 1.15 113.1 107 6.36 6.31 1.124 1.4834 at 24---. 01s

ou momo monomm cowmcno n 16.-- 0 Om 1.45 93.3 5.28 1.5335at24.--- 011mncmonrwoGcm) I CO(CHzCHO).H]

l O(JJHOHzO);P(O)(O-CH;) I c 0 cH,cH0).H

17..." '0 on; H 1.38 126.2 132.0 668 6.79 0.01

mcnomoniwo cowmonohn 1a Br 1. 21

Br 0( HCH0).P(0)(0CH1):

B CO(CH:CHO),H

10-.--- C1 0 1.0 3.82 ass 1.4958at 000 01 llowmcmo monommm (1-01 01cowmcmomi Phthalic anhydride, 296.2 parts, 82.0 parts of phosphorus acidand 0.04 part of sodium formate were placed in a pressure apparatusequipped with a stirrer, thermometer and oxide addition means, and themixture was heated to 70 C. 548.5 parts of propylene oxide was added tothe mixture, with stirring, over a period of 4% hours, the temperaturevarying from about 90' C. to 134 C. The reaction mixture was thenstirred for 5 hours at 120- 125' C., after which the excess oxide wasremoved by stripping at 120-125 C. at mm. of Hg, giving a slightlyyellow, viscous product having the following properties: P (calculated)3.44%; P (found) 3.35%. Total acid, 8.17 mg. KOH/gm.]

Additional compounds, summarized in the following table, were prepared[by a process similar to that outlined in Example 20.]

Total 1253/ 1 percent Density Refractive 1rd?) Compound new. Calod.Found Caled. Found index at'C. gm.

i. 0 OH. "I (311: 1.34 158.9 161.5 4.42 4.11 5:8:;:-I.;;:i;::;2.i53=0.11]

OdiKCHsO). P=O

CO(CH:CHO);H L 3 (EH: 1 [3].- O OH: OC|H L85 1404 168.5 4.8 4-05::.-.'===r. l.5080at2l.;:= 0J3 OGBHCHsO): =O

CO(CH!CHO);H L s B OCH; L21 :i t 0 em l B pJOKBHGHsO): =0

Br cowmcnoms L 3 I511:

Br s m1- 0 001;. 1.0

O( H: Hs0)x i=0 CO(CH:CH:):H

1i m... O CH: 1.75 H5 151 2.84 2.98 37:33:22: Lmstm" La] (O(JHCHs);0-P=O00(CH3CHOMHJ Ht 1 As is apparent from the generic formula set forthhereinbefore, reaction products of mixtures of phosphoric acids (such asthose obtained from the reaction of alcohols or phenols with P 0 withanhydrides and oxides are embodied herein. This is in addition to theindividual members of the mixtures which are set forth in the exampleswhich follow.

EXAMPLE [26] 23 tcntomww 0 cntncmc G CHaOPWNOH):

0 cm pso(oncmo)- wxocmg 01-! (calculated), 146 mg. KOH/gm.; OH (found)149 mg. KOH/ gm.

P (calculated), 5.4%; P (found), 5.08%

Density 20/ 4, 1.235

Specific gravity at 24 0, 1.5006

Total acid, 0.16 mg. KOH/gm.

The following table summarizes other mixtures obtained by processessimilar in all material respects to Example [26.] 23.

--- Deuslt Refractive K I Compound ug. Cnlcd. Found Caled- Found 204lads: atO. gm.

[271.2 0 CH; L8 171 160.5 6.82 6.25 1.238 1.4Bat25.5 0.37

- 0(41HCH|0)-P(0)(0OH:)1

H --CO(OH|CHO)H plus 0 CH: HCgO($HGH:O); -P(O)OOH; H -CO(OH;CHO);HJI

[3].. 0 CH: 1.2 158 5.85 5.52 1.175 LMBMZLH: 0.15

110- O(HCHaO)|P(O)(OU4H H C0(CH;CHO)H plus B CO(CH:CHO).H

B CO(CH:CHO);H

.. 1' Ha I [30]-- 0 CH; 1. I8 115 4. 4.16 1. 217 1.4875 at $5.. 0. 2i

0(2HCHnO)zP(O) (000 111):

O O (CILOHOJJI plus C0(CH:OHO);H

5391] O CH: 1.19 132.5 147.5 5.10 4.09 1.101 1.4610 It 20.--. 0.21

HC-MHOIhOhHO)(OOnHu-l):

HC-CO(CH CHO)|H plus 0 0H: HC-EOJJHCILO) P(O)OCnH11-l H-C0(CH:CHO):H]

III

TABLE- ContinueG Total H, mg. acid, KOH/gm. P, Percent In Density,Refractive KOIf/ Compound 1, avg. Cslcd. Found Calcd. Found /4 index atn 0. gm. [29 ('1; 0.94 143 131.5 5. 47 5. 53 0.15

00 (cntcmo ,r o (oom) C O (CHaCHaO) E plus do cinema) 1 P (0) oom C O(CHaCHzO) 1H E3031" CH: 1. B 118 83 4. 55 4t 52 1.

do (daemon? o) (oon.)

C O (CHICHO):H

plus

- O CH:

dou snomo), rtmoorn ("30(CH:CHO),H L 0 H: a

0 C 1.3 135 111 5. 1B 5. O7 0. 19

Other new and useful compounds may be prepared from the compounds ofExamples 12-[31] 28 by reacting one or more of the reactive centersthereof with a compound of the formula M,P(O) Hal, wherein M and Hal areas hereinabove defined, substantially as follows.

CH: (Compound 0! Example 12) COWHaCHOhPWX This type of compound may alsobe obtained from oxyalkylated dicarboxylic acids and the appropriatechloridate. Thus, by reacting 373 parts of 0 E0 (UIh HI kuH C 0 (CHICHIO)uiH in methylene chloride with 146.2 parts of (CH O),P(O)Cl at 10 C. orbelow, there is obtained the compound C0 (CHaOHaOhmP (0) (001-15)!having a total acid number of 0.55 and a refractive index of 1.4966 at25 C.

Additional non-limiting examples of this general class compounds aresummarized in the following table.

Moles o! R! R! i 0 Hal 1 0 Hal Compound 0! Example B R 13 (CsHa0)|P(O)Cl1 7 pounds contemplated, and it is not to be considered as a limitationon the invention with respect thereto.

In this compound, C(CH corresponds to W, defined hereinabove, and isderived from tetravalent pentaerythritol. Other radicals which are atleast divalent may be derived from ethylene glycol, propylene glycol,butylene glycol, glycerol, trimethylol ethane, trimethylol propane, andsimilar compounds.

The new compounds, especially those containing at least one activehydrogen per molecule, have been found to be useful as flame retardantsfor polyurethane foams and resins. They markedly improve the flameproperties of polyurethanes without any adverse effect on the polymeritself. The degree of fire-retardance will depend upon the amount ofphosphorus per se in the finished polyurethane, but as a generalstatement the compounds of the present invention will be effective atphosphorus concentrations of about 0.5% to about 5.0%, with thepreferred amount falling with the range of from about 1.0% to about3.0%.

Briefly, in using the active hydrogen-containing compounds of theinvention to obtain fire-retardant polyurethanes, the compound, or amixture thereof with a normally used polyol, is mixed with a catalystand a surfactant, and this is blended with a polyisocyanate, whereuponreaction occurs to produce a polyurethane polymer. If a foam is desired,a slight excess of polyisocyanate will be present in the mixture to bereacted with water (which produces CO upon reaction with the excess NCO,thereby supplying the foaming agent). As an alternative, stoichiometricNCO may be used, and a low boiling inert liquid, such as achlorofluorocarbon, may take the place of the internally produced CO Inusing the compounds of this invention which contain active hydrogenswith conventional polyols, it will be obvious to those skilled in thisart that the substitution must be done on the basis of active hydrogenequivalents. That is, the amount of phosphorus compound substituted mustcontain an amount of active hydrogen equivalent to that in the removedconventional polyol.

The polyisocyanates which are useful are those which are well-known inthe polyurethane art, and no elaborate discussion of them is believednecessary. As examples, however, the following polyisocyanates may beused to advantage with the inventive compounds. They are: tolylenediisocyanate (a commercial mixture of the 2,4- and the 2,6-ismers);polymethylene polyphenyl isocyanate, having the formula at a where n isgreater than zero; hexamethylene diisocyanate;naphthalene-1,S-diisocyanate; naphthalene triisocyanate; dichlorodiphenyl methane diisocyanate; dimethyl diphenylmethane diisocyanate,and other aromatic or aliphatic polyisocyanates containing 2 or morefunctional or isocyanate groups.

The example which follows will illustrate the usefulness of thecompounds of this invention as flame retardants for polyurethane foams.

EXAMPLE [35] 32 One hundred and eighty-four parts of propoxylatedsucrose having about 1.2 oxypropylenes per equivalent of hydroxyl, 139parts of the mixture of Example [27,] 24, 4 parts of a silicone-typesurfactant L-5310, 3 parts of triethylenediamine catalyst and 87 partsof trichlorofluoromethane were blended together by stirring. To thismixture was added 250 parts of PAP] (polymethylene polyphenylisocyanate), and this total mixture was stirred vigorously for 23seconds and poured into a container for foaming. The foam was fullyrisen and tack free in 98 seconds. It was allowed to stand overnight.

The product, a rigid foam, was fine-celled, and had a density of 2.5pounds per cubic foot. It had good hydrolytic and dimensional stabilityat both high humidities (up to 100%) and high temperatures (l00-l20 C.).The foam burned less than one inch when tested according to ASTM D-l692.

A control, prepared from the agents of this example, less thephosphorus-containing compound, was non-selfextinguishing when tested inaccordance with ASTM D-l692.

In addition to their utility as flame retardant agents forpolyurethanes, the chemicals of this invention are also useful as flameretardants and plasticizers for vinyl resins, polyesters, and the like.

It is understood that various other modifications will be apparent toand can be made by those having skill in this art without departing fromthe spirit and scope of the invention. Accordingly, it is not intendedthat the scope of the claims appended hereto be limited to thedescription and examples set forth herein, but rather that the claims beconstrued as encompassing all of the features of patentable noveltywhich reside in the present invention, including all features whichwould be treated as equivalents thereof by those skilled in the art towhich the invention pertains.

With respect to the value of x in Examples 12 through [31,] 28, it willbe further understood that the value assigned may not be the exactnumber of oxyalltyl units attached at the designated center. The valuesgiven for x in the various compounds, however, will not vary widely fromthese actual values. Each x was determined by dividing the totalequivalents of alkylene oxide reacted by the number of equivalents ofacid hydrogen in the reaction mixture. As an illustration, in Example 13a total of 2.58 equivalents of ethylene oxide reacted, and this wasassumed to be divided equally between the two acid hydrogenspresent--one from the phosphorus moiety and one from the opening of theanhydride ring. Thus x is an average value which, when multiplied by thenumber of xs in the molecule, will enable one to determine the actualamount of oxyalkyl present in the chemical in question. The values of xin the appended claims are to be interpreted in view of thisexplanation.

We claim:

1. An organo-phosphorus compound selected from the formulas wherein Dand x are as hereinafter defined R is a member of the group consistingof hydrogen, alkyl containing from 1 to 18 carbon atoms, and phenyl;

R" is a member of the group consisting of alkyl containing from 1 to 13carbon atoms and (lower) alkoxy (lower) alkyl;

A is the nucleus of a member selected from the group consisting ofaromatic dicarboxylic acid anhydrides and aliphatic dicarboxylic acidanhydrides;

D is a member of the group consisting of hydrogen,

lower alkyl, and chloro (lower) alkyl;

F is a member of the group consisting of hydrogen and ($3M G is a memberof the group consisting of hydrogen and 1 wherein R and R are ashereinbefore defined, and

a and b are as defined hereinafter;

a and b are each 0 to 2, their sum being 2;

r, s, and t are, respectively, 0 to 2, 0 to 2 and 1 to 3,

their sum being 3;

W is the hydrocarbyl nucleus of a polyhydroxy compound containing from 2to 4- hydroxyls;

x has an average value of from about 1.0 to about 5.0;

and

z is an integer corresponding to the number of hydroxyls in W[.],

provided that where G is hydrogen, .9 is at least 1.

2. The compound of claim 1 wherein A is the nucleus of a dicarboxylicacid anhydride selected from the group consisting of (1) phthalic,halogen-substituted phthalic, nitro substituted phthalic, alkylsubstituted phthalic, homophthalic, naphthalic, (2) adipic, azelaic,glutanic, snberic, itaconic, pimelic, succinic, maleic, (3) thehalogen-substituted and alkyl-substituted members of the aforesaid group(2), (3) chlorendic, hydrophthalic, and endomethylene phthalicanhydrides.

3. An organo-phosphorus compound selected from the formulas 0 ion" (B!)-|-CO(CH;CHO),-P(O) (R'), O D t (i F 0 HCH;O J) I t R).

-cowmcnono and FOR D O (ilP (O) (OCHIAlH) -O F [O CHCHah-O 0 R is amember of the group consisting of (lower) alkoxy (lower) alkyl, alkylcontaining from 1 to 18 carbon atoms, aryl, alkyl-substituted arylwherein the alkyl contains from 1 to 18 carbon atoms, chlorosubstitutedaryl, bromo-substituted aryl, aralkyl, and

wherein D and x are as hereinafter defined;

R is a member of the group consisting of hydrogen, alkyl containing from1 to 18 carbon atoms, and phenyl;

R" is a member of the group consisting of alkyl containing from 1 to 13carbon atoms and (lower) alkoxy (lower) alkyl;

A is the nucleus of a member selected from the group consisting ofphthalic, chloro-substituted phthalic, bromo-substituted phthalic,iodo-substituted phthalic, nitro-substituted phthalic, alkyl-substitutedphthalic wherein the alkyl contains from 1 to 12 carbon atoms,homophthalic and naphthalic anhydrides;

D is a member of the group consisting of hydrogen,

CH3, C2H5 and F is a member of the group consisting of hydrogen and G isa member of the group consisting of hydrogen and wherein R and R are ashereinbefore defined, and

a and b are as defined hereinafter; a and b are each 0 to 2, their sumbeing 2; r, s, and t are, respectively, 0 to 2, 0 to 2 and 1 to 3,

their sum being 3; W is the hydrocarbyl nucleus of a polyhydroxycompound containing from 2 to 4 hydroxyls; x has an average value offrom about 1.0 to about 5.0; and z is an integer corresponding to thenumber of hydroxyls in W. provided that where G is hydrogen, [S] is atleast 1.

4. The compound of claim 3, Formula 2, in which 1' is 0, R is methyl, Gis hydrogen, D is CH and A is the nucleus of tetrabromophthalicanhydride.

5. The compound as defined in claim 4, having the C O (CHzQHOhH Br CH: 3

Br CH; 1

7. The compound of claim 4, having the structure B1 CH: Br 930(61101-130IJ P(O)(OCHJ)I 9. The compound of claim 1 wherein A is the nucleus of amember selected from the group consisting of hydrophthalic,endomethylene phthalic, camphoric, -norbornene-2, and chlorendicanhydrides, and D is a member of the group consisting of hydrogen, CH C--H and CICHg.

10. The compound of claim 1, having the structure or 0 o hocmcmo-rtoxoonn),

l C1-C1 Cl I cocincrnon 11. The compound of claim 1 wherein A is thenucleus of a member selected from the group consisting of: (1) adipic,azelaic, glutaric, suberic, itaconic, pimelic, and succinic acidanhydrides; (2) the chloro-substituted members of (1); and (3) thealkyl-substituted members of (I), wherein alkyl contains from 1 to 12carbon atoms; and D is selected from the group consisting of hydrogen,CH3, CQH5, and ClCH 12. The compound of claim 1, Formula 2, wherein r is0, R is methyl, G is hydrogen, D is CH; and A is the nucleus of maleicanhydride.

13. The compound as defined in claim 12, having the structure 0 CH: IHobo(bHcmo),-P(0)ooH, H -oo(oH,oH0),H 2 14. The compound of claim 12,having the structure 0 CH; Ito-b0(bHcm0)1.=-P(o)0cHi H 0o oH,oHO)|.iHJCH1 2 15. The compound as defined in claim 12, having the structure OCH: H0-bo(bHoH=0),-P(0)(oonur H oo(oH,oH0),H

6H. 16. The compound of claim 12, having the structure [17. A processfor the manufacture of an organo-phosphorus compound as defined in claim1, Formulas 2 and 3, which comprises the simultaneous reaction of theappropriate phosphorus compound having at least one acid function, adicarboxylic acid anhydride having A as its nucleus, and a compoundselected from the group consisting of ethylene oxide, propylene oxide,butylene oxide and epichlorohydrin.]

[18. A process for the manufacture of an organophosphorus compound asdefined in claim 3, Formulas 2 and 3, which comprises the simultaneousreaction of the appropriate phosphorus compound having at least one acidfunction, a dicarboxylic acid anhydride selected from the groupconsisting of phthalic, chloro-substituted phthalic, bromo-substitutedphthalic, iodo-substituted phthalic, nitro-substituted phthalic,alkyl-substituted phthalic wherein the alkyl contains from 1 to 12carbon atoms, homophthaiic and naphthalic anhydrides, and a compoundselected from the group consisting of ethylene oxide, propylene oxide,butylene oxide, and epichlorohydrin.]

[19. The process as defined in claim 18 wherein the compound producedfalls within Formula 2 in which r is O, R is methyl, G is hydrogen, D isCH and A is the nucleus of tetrabromophthalic anhydride] [20. Theprocess as defined in claim 19 wherein the organo-phosphorous compoundobtained is Br 0 CH; B. Miscellanea [22. The process as defined in claim19 wherein the organo-phosphorus compound is [23. The process as definedin claim 22 wherein at is 1.2.]

[24. The process as defined in claim 18 which comprises mixing thedicarboxylic acid anhydride and phosphorus compound, subsequently addingthereto an excess of said oxide at a temperature of from about 70 C. toabout C., heating at a temperature sufliciently high to completeneutralization of the carboxyl acid functions formed, but not higherthan about C., and then removing the excess oxide from the saidorgano-phosphorus compound] [25. The process of claim 18 which comprisesthe steps of mixing the dicarboxylic acid anhydride and phosphoruscompound and subsequently adding said oxide thereto, the oxide being inexcess of the amount necessary to react with all of the acid functionsof the said phosphorus compound and the subsequently formed carboxylgroup, at temperatures sufiiciently high to react the said oxide and thesaid acid functions, and removing the excess oxide from theorgano-phosphorus compound thus formed] 26. An organo-phosphoruscompound formula 0 boa" (R'). LOO(CH,CHO) (O) D r( lh wherein:

R is a member of the group consisting of (lower) alkoxy (lower) alkyl,alkyi containing from 1 to 18 carbon atoms, aryl, alkyl-substituted arylwherein the alkyl contains from I to l 8 carbon atoms,chloro-substituted aryl, homo-substituted aryl, aralkyl, and

wherein D and X are as hereinafter defined,

R is a member of the group consisting of hydrogen, alkyl containing from1 to 18 carbon atoms, and phenyl;

R" is a member of the group consisting of alkyl conraining from I to 13carbon atoms and (low'er) alkoxy (lower) alkyl;

A is the nucleus of a member selected from the group consisting ofaromatic dicarboxylic acid anhydrides and aliphatic dicarboxylic acidanhydrides;

D is a member of the group consisting of hydrogen,

lower alkyl, and chloro (lower) alkyl;

0 and b are each 0 to 2, their sum being 2; and

z has an average value of from about 1.0 to about 5.0.

27. An organo-phosphorus compound of the formula:

F OCHCI'I: 0G t wherein:

R is a member of the group consisting of (lower) all:-

oxy (lower) alkyl, alkyl containing from I to 18 carbon atoms, aryl,alkyl-substituted aryl wherein the alkyl contains from 1 to 18 carbonatoms, chloro-substituted aryl, bronze-substituted aryl, aralkyl, and

D (CHh3HO);H wherein D and x are as hereinafter defined;

R is a member of the group consisting of hydrogen, alkyl containing fromI to 18 carbon atoms, and phenyl;

" is a member of the group consisting of alkyl containing from 1 to 13carbon atoms, and (lower) alkoxy (lower) alkyl;

A is the nucleus of a member selected from the group consisting ofaromatic dicarboxylic acid anhydrides and aliphatic dicarboxylic acidanhydrides; D is a member of the group consisting of hydrogen,

lower alkyl, and chloro (lower) alkyl; F is a member of the groupconsisting of hydrogen and R) wherein R and R are as hereinbeforedefined, and

a and b are as defined hereinafter; a and b are each 0 to 2, their sumbeing 2; W is the hydrocarbyl nucleus of a polyhya'roxy compoundcontaining from 2 to 4 hydroxyls; x has an average value of from about1.0 to about 5.0,-

and z is an integer corresponding to the number of hydroxyls in W.

References Cited The following references, cited by the Examiner, are ofrecord in the patented file of this patent or the original patent.

UNITED STATES PATENTS 3,419,642 12/1968 McGary et al. 260 -952 3,092,5436/1963 Richter 260952 X LORRAINE A. WEINBERGER, Primary Examiner R. L.RAYMOND, Assistant Examiner US. Cl. X.R.

252-8.); 2602.5 FP, 77.5 AR, 453 AM, 928, 929, 930, 971, 973, 978

um'rsn sums PATENT omcr: CERTIFICATE OF CORRECTION a April 16, 197AIo-wau (5/09) Paton: No. R 7,9 9

humor) Vasco G. Camacho, James J. Anderson 80 Wendell M. Byrd I: incertified that error appura in the above-identified patent and that aidLetters Patent are hereby corructsdDaa shown below:

D H H l i CH should read --CH--. line &5, "abve" should read --ahove--.line 23, "hydroyls" should read --hydroxyls--. line 7, 2,2,2)" shouldread "(2,2,1)". line 5, and other alkyl-substituted) should --(and otheralkyl-substituted phthalics Where the alkyl has from 1 to 12 carbonatoms line 52, "dialkyl' should read -dialkyl--. line 67, "RP O)OH(OR')"should read --R"l (O)(OH) line 36-87, 'were placed in means for coolingshould read --were placed in a reaction vessel provided with a stirrer,thermometer and means for cooling;--. line A l, "1000 parts of each washshould read 1000' parts for each wash--.

Column 1, line 59, Column 3, Column 5, Column 5, Column 5,

read

Column 5, Column 5, Column 6,

Column 6,

Signed and sealed this 8th day of October 1974.

(SEAL) Attest:

C. MARSHALL DANN Commissioner of Patents McCOY M. GIBSON JR. AttestingOfficer

